CA1110647A - N-substituted bis-carbamoyl sulfide compounds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Compounds of the formula:

wherein:
n is 1 or 2;
R1 is fluorine or X is sulfur, sulfinyl or sulfonyl;
R2, R3, R4, R5, R6, and R7 are individually alkyl having from 1 to 8 carbon atoms.
The compounds of this invention are useful for controlling insects, mites and nematodes.

Description

~lQ647 D-10,990 This invention relates to novel N-substituted bis-carbamoyl sulfide compounds and to their preparation.
This invention is also directed to insecticidal, miticidal and nematocidal compositions comprising an acceptable carrier and an insecticidally, miticidally or nematocidally effective amount of a compound of this invention as well as to a method of controlling insects, mites and nematodes by subjecting them to an insecticidally, nematocidally or miticidally effective amount of a compound according to this invention. In another limited aspect this in-vention relates to a limited group of compounds, that in addition to their pesticidal activity are also useful intermediates in the preparation of other pesticidally active com~ounds.
More particularly, this invention relates to ~; com~ounds of the fonmula:

~t~ ~1 1 , "
` ~ R3-C=NC-N-S-N-C-Rl .:
S,()n .:;' R2 wherein:
n is 1 or 2;
R is fluorine or -0-N=C-R7 ;., ~ 1 ~ X-R~
.~, u X is sulfur, sulfinyl or sulfonyl;
R2, R3, R4, R5, R6 and R7 are individually alkyl.

The compounds of this invention exhibit outstand-ing insecticidal, miticidal and nematocidal activity. The com~ounds of this invention are also characterized by "',.
.. ' :.

D-10,990 substantially reduced mammalian toxicity and phytotoxicity in comparison with known pesticidally active compounds hav-ing a comparable spectrum of insecticidal, miticidal and nematocidal activity.
In general 2~ R3, R4~ R5~ R6 and R7 sub-stituents individually may not include more than eight carbon atoms. Preferred because of their higher level of pesticidal activity are the compounds of this invention in which R2, R3, R4, R5, R6 and R7 substituent individually include from 1 to 5 carbon atoms. Particularly preferred compounds are those wherein R3, R4, R5 and R7 are methyl-Other preferred compounds according to this invention are those in which Rl i8 fluorine, due to their additional utility as intermediates in the preparation of pesticidally active compounds by reaction with oxime compounds, hydroxylated aryl compounds ~r other active hydrogen -containing compounds. For example, l-methylsulfinyl-. .
acetaldehyde Q-[N-methyl-~-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamovl]oxime may be reacted '

2,2-dimethyl-2, 3-dihydro-7-hydroxybenzofuran in the presence of triethylamine as an acid acceptor to yield N-ll-methylsulfinylacetaldehyde-0-~N'-methylcarbamoyl)oximel-~-[2, 2-dimethyl-2, 3-dihydro-7-(N'-methylcarbamoyloxy)benzo-furan] sulfide,the corresponding pesticidally active carbamate compound.
The compounds of this invention can be prepared in accordance with a variety of methods. One preferred method for preparing compounds ln which Rl is fluorine is illustrated by the general reaction scheme set forth ';' ,. ~

3.

.

D-10,990 below in which n, R2, R3, R4 and R5 are as described above:

METHOD I
lol ,R5 ,R4 o ,R3 ,0, R4 ,5 ,0, F-C-N -S-N -N-F + HON=C-S(0)n-R2 -~ R3-C=NOC-N -S-~ -C-F
S()n The compounds of this invention in which Rl is other than fluorine can be prepared by reacting the reaction : product of Method I, usually in situ, with an appropriately substituted oxime compound as illustrated in the reaction scheme set forth below in which n, R2, R3, R4, R5, R6 and R7 are as described above:

METHOD II
0 R4 R50 IR4 ,R50 R3-C-NOC-N-S-N-C-F + HON=C-R7~ R -C=NOC-N-S-N-CON=C-R7 S~)n X-R6 R2-S()n X-R6 :. 2 An alternative method of preparing compounds of this invention in which R3=R7, R2~R6 and X S()n illustrated by the general reaction scheme set forth below in which R2, R3, R4, R5 and n are as described above:

METHOD III
0 R4 R50 ,3 O ,R4 ,R50 FC-N-S-N-CF + 2 HON=C-S(0)n-R2. ,R3-C--NOC-N-S-N-coN=c-R3 S(~n~R2 ( )n 2 . .

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1~10~47 D-10,990 The reactions of Methods I and II are carried out by bringing together substantially equivalent amounts of the reactants in an inert solvent. In the reaction illustrated in Method III,two equivalents of the oxime reactant is reacted with one equivalent of the bis-carbamoyl fluoride reactant in an inert solvent.
Illustrative of inert solvent that are useful in the conduct of these reactions are benzene, toluene, methylene chloride, xylene, dioxane, tetrahydrofuran or the like.
Reaction temperatures are not critical and can be varied over a wide range depending to a large extent on the reactivity and the thermal stability of the reactants.Preferred reaction temperatures are from about -30C. to about 100C.
Reaction pressures are not critical. For convenience the reaction is usually conducted at atmospheric or autogeneous pressure.
These reactions are conducted in the presence of an acid acceptor. The molar ratio of the acid acceptor is usually equivalent to that of the oxime compound present in the reaction mixture although a slight excess of the acid acceptor may be used if desired. The acid acceptor may be either an organic or an inorganic base. Illustrative of organic bases that are useful as acid acceptors are tertiary amines, alkali metal alkoxides or the like.
Bases such as sodium hydroxide, potassium hydroxide or the like are illustrative of inorganic bases that are useful. Preferred organic acid acceptors are tertiary amines such as triethylamine, pyridine, trimethylamine, 1, 4-diazobicyclo 12.2.2] octane or the like.

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D-10,990 These reactions can be conducted in a homogeneous (mono) phase system, or when an inorganic base i9 employed as the acid acceptor, in a heterogeneous phase system.
In the latter case phase transfer agents such as crown ether compounds, quaternary ammonium halide compounds or the like may be used to facilitate the transfer of the reactants across the phase interface. For example, when a solid inorganic ~ase is employed as an acid acceptor in an organic solvent medium a crown ether compound may be used as a phase transfer agent, or alternatively when these reactions are conducted in a two-solvent phase system, which consists of.
an aqueous solution of an inorganic base acid acceptor as one phase and an organie solvent containing dissolved reactants as the other phase, a quaternary ammonium halide compound may be employed as the phase transfer agent.
Compounds of this invention in which n is 1 or ' 2 and/or X is either a sulfinyl or a sulfonyl group can be prepared by the reaction illustrated in Methods I, .: II, and III. An alternative method of preparing compounds in which X=S(0)n is by selectively oxidising the bis-alkylthio compound with an oxidising agent, as for exam~le per-acetic acid or other organic peracids as illustrated in the following reaction scheme in which n, R2, R3, R4, R5, R6 and R7 are as described above:
:
METHOD IV

0 R4 R50 organic ,0, R4,R5,0, R3-C=NOC-N-S N-CON~C,-R7 p-r ~ R3-C-NOC-NSN-CONsC-R7 2 S-R6 S()n R2 S()n~R6 , .
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Oxime compounds utiliz~ as reactants in the pre-paration of the compounds of this invention can be prepared according to a variety of methods. For example, 1-methylthioacetaldoxime can be prepared by reacting acetaldehyde with hydroxylamine hydrochloride to form acetaldoxime which is then treated with chlorine in hydrochloric acid solvent to form l-chloroacetaldoxime which is then further reacted with sodium methylmercaptide to form the desired aldoxime compound. l-Methylthioaldoxime is readily converted to the l-methylsulfinyl and l-methyl-sulfonyl derivatives by oxidation with peracetic acid.
The above disclosed method together with other methods for preparing oxime comp~unds are described in more detail in Vnited States Patent Numbers 3,752,~
3,726,908; 3,843,669; and Belgian Patent 813,206 and 815,513.
8is -[N-Alkyl-N-fluorocarbonylamino)sulfide compounds used as reactants in the preparation of the compounds of this invention can be conve~iently prepared ' 2~ by a variety of methods. One preferred method consists of reacting hydrogen fluoride with an appropriately substituted alkylisocyanate compound to form the corresponding alkylaminocarbonylfluoride compound which is then reacted with sulfur dichloride (SC12) in the presence of at least two equivalents of an acid acceptor as described above, preferably in an inert solvent, to yield bis-(N-alkyl-N-fluorocarbonylamino)sulfide compound.
The following specific examples are presented to more particularly illustrate the manner in which the compounds of this invention can be prepared.

; 7.
, , 111~647 D-10,990 EXAMPLE I

Preparation of N, N'-bis-(N-methyl-N-fluorocarbonylamino)sulfide To a polyp~opylene reactor containing 80 g (4.0 m) of hydrogen fluoride in 1800 ml of toluene, cooled to -40C was added dropwise with stirring 228 g (4.0 m) of methylisocyanate, over a period of 20 min. The reaction mixture was allowed to warm to 0C and was maintained at this temperature for 1 hr. Then 60 g (2 m) of freshly distilled sulfur dichloride was added followed by a slow addition of 346 g (4.4.m) of pyridine at -20 to -0C.
After stirring for 2 hrs. at -10C and for 16 hrs. at ambient temperature, the reaction mixture was diluted with S00 ml of water. The toluene layer was further washed with (3 x 500 ml) water dried and distilled to yield 244 g (66 percent) of the product. B. P. 55-57C/
0.25 mm. m.p. 40-41C.
Calc'd for C H F N 0 S: C, 26.09; H, 3,28; N, 15.21

4 6 2 2 2 Found: C, 26.19; H, 3.20; N, 14.79 , EXAMPLE II
Preparation of l-Methylsulfinyl-lN-methYl-N-Oi~cthy____-fluorocarbonyla inosulfenyl) carbamoyloxyr acetimidate To a solution of 4.0 grams (0.033 m~ of methyl-,~j, sulfinyl-N-hydroxyacetimidate and 6.07 grams (0.033m) of N, N'-b -(N-methyl-N-fluorocarbonylamino) sulfide in 100 ~ ml of toluene was added dropwise with stirring 3.34 grams ; (0.033 m) of triethylamine dissolved in 50 ml of toluene.
i:
After stirring overnight the solid was filtered (desired material contaminated with bis-carbamate). The filtrate was washed with water, dried and concentrated to afford 0.5 grams of the product. Total weight of purified 8.

D-10,990 material from both crops was 1.55 grams, m.p. 120-125C
(decomp.).
Infra red (KBr) 5.55 (C0), 5.78 (C0)~
NMR (CDC13) ~ 2.36 (s), 3H, CH3; 2.85 (s), 3H, CH3S0; -3,43 (s~, 6H, CH3N.

EXAMPLE III

Preparation of S-Methyl-N- N'[N"-(L-meth lsulfi oxycarbonyl)-N"-methy~aminosulfenyl~-N'-methylcarbamoy oxy t loacet ate A mixture containing 2.42 grams ~0.02 m) of methylsulfinyl-~-hydroxyacetimidate, 5.5 græms (0.02 m) of S-methyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonylamino-~ulfenyl)-carbamoyloxy]thioacetimidate, and 2.02 grams (0.02 m) of triethy~lamine in 100 ml of toluene was heated at 50-~0C for 4 hours and then stirred overnight at room --temperature. The solid was filtered and taken in methylene chloride. The organic solution was washed with water, ;~ dried and concentrated to a residual solid. On recrystalliz-~;~ ation from ethylacetate-methylene chloride it afforded 3.8 grams of the solid m.p. 140-141CC.
Calc'd for CloH18N45S3 C, 32.34; H, 4.90; N, 15.12 Found: C, 32.41; H, 4.91; N, 14.86 EXAMPLE IV
reDaration of S-Methyl-N-[N'-lN"-(l methylsulfonYlethyl-idiniminooxycarbonyl)-Nl~-methyIaminosulfeny~ r-meth carbamoyloxy]-th~oacetimidate ' To a suspen8ion of 5.26 grams (0.019 m) of . ~ .
.; approximately 95 perce~t S-methyl-[N-methyl-N-(N'-methyl-, N'-fluorocarbonylaminosulfenyl)carbamoyloxy]thioacetimidate and 2.61 grams (0.019 m) of methylsulfonyl-N-hydroxyacetimidate .

.. 9.

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D-10,99Q

in 100 ml of toluene was added with stirring 1.92 grams ~0.019 m) of triethylamine diluted in 50 ml of toluene.
After stirring for 3 hours at room temperature the solid was filtered. Recrystallization from chloroform ethyl alcohol afforded 5.0 grams of the product. m.p. 120-123C.
Calc'd for CloH18N46S3: C, 31.08; H, 4.69; N, 14.50 Found: C, 30.95; H, 4.79; N, 14.22 EXAMPLE V
Preparation of l-MethYl-N-~N'-[N"-(l-mct~
ethylidiniminooxycarbonyl)-N"-methylaminosul eny N'-meth~lcarbamoyloxyl-sulfinylacetimldate To a solution of 8.0 grams (0.07 m) of ~thyl-sulfinyl-N-hydroxyacetimidate and 6.45 grams (0.035 m) of N, N'-bis-(~-methyl-N-fluorocarbonylamino)sulfide in 100 ml of toluene was added dropwise 7.08 grams (0.07 m) of triethylamine. After about 15 minutes a white solid started precipitating. After stirring at room temperature for 18 hours, the solid was filtered, taken in methylene chloride. The organic solution was washed with water, - dried and concentrated to a residual solid. On recrystallization from methylene chloride toluene it ; afforded 5.4 grams of a white solid. m.p. 131-134C.
calc'd for CloH18N46S3: C, 31.08; H, 4.69; N, 14.50 Found: C, 31.35; H, 4.54; N, 13.94 (METHODIv) To a solution of 5.0 grams (0.014 m) of S-methyl-N-[N'-[N"-(l-methylthioethylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxy]-thioacetimidate in 75 ml of ethylacetate was added 12.46 grams of 25.6 percent solution of peracetic acid in ethylacetate. After 10 .

6~7 D-10,990 stirring for 16 hours at room temperature the soLid was filtered to afford 7.0 grams of the product. The melting point and spectral data was identical to the product obtained by Method I.

EXAMPLE VI
Preparation of l-MethylsulfonYl-N-[N'- ~'~ methylsulfonyl-ethylidiniminooxycarbonyl)-N"-methylamlnosu ~enyl~-N -methyIcarbamoyloxyl-acetiml ate To a solution of 5.0 grams (0.0365 m) of methyl-sulfonyl-N-hydroxyacetimidate and 6.72 grams (0.0365 m) of N, N'-bis-(N-methyl-N-fluorocarbonylamino)sulfide in 150 ml of toluene was added 3.69 grams (0.0365 m) of triethylamine. After stirring for 16 hours, the solid was collected by fil.tration to afford after crystallization ; 1.1 grams of a white solid m.p. 173-175C (decomp.).
The filtrate was predominaritly the monoadduct S-methyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyl-oxy]-sulfonylacetimidate.
Calc'd for CloH18N4~8S3 C, 28.70; H, 4.33; ~, 13.39 Found: C, 28.64; H, 4.31; N, 13.29 .... .
The following compounds are representative of other compounds that are within the scope of this invention that can be prepared accordi~g to this invention by selecting ; ~ appropriate starting materials for use in the procedure described herein above:
l-Isopropylsulfinyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)carbamoyloxy] acetimidate;
l-pentylsulfonyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)carbamoyloxy] acetimidate;

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6~7 D-10,990 S-Isopropyl-N-[N'-[N"-(l-methylsulfinylethylidiniminooxy-carbonyl)-N"-methylaminosulfinyl]-N'-methylcarbamoyloxy]
thioacetimidate;
~-Isopropyl-N-[N'-[N"-(l-isopropylsulfinylethylidiniminooxy-carbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxy]
thioacetimidate;
S-lsopropyl-N-~'-[N"-(l-isopropylsulfonylethylidiniminooxy-carbo~yl)-N'-methylaminosulfenyl]-N'-methylcarbamoyloxy3 thioacetimidate;
l-Isopropylsulfonyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonyl-aminosulfenyl)carbamoyloxyl acetimidate;
l-Butylsulfinyl-[N-methyl-N-(N'-methyl-N'-1uorocarbonyl-aminosulfenyl)carbamoyloxy] acetimidate.
Selected species of the new compounds were evaluated to determine their pesticidal activity against mites and certain insects, including an aphid, a caterpillar, a beetle and a fly.
Suspensions of the test compounds were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxy polyethoxy-ethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 150 milliliters of water to give roughly ~00 milliliters of a suspension containing the compound in finely divided form. The thus-prepared ætock suspension contained 0.5 percent by weight of test compound. The test concentrations in parts per million by weight employed in the tests described hereinbelow were obtained by appropriate dilutions of the stock suspension with water. The test procedures were as follows:
Bean APhid Foliage Spray Test Adults and nymphsl stages of the bean aphid (Aphis fabae Scop.) reared on potted dwarf nasturt~m plants at 65-70F and 50-70 per cent relative humidity, D-10,990 constituted the test insects. For testing purposes, the number of aphids per pot was standardized to 100-150 by trimming plants containing excess aphids.
The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation.
The potted plants (one pot per compound tested) infested with 100-150 aphids, were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which lasted 25 seconds, was sufficient to wet the plants to run-off.
As a control, 100-110 milliliters of a water-acetone-em~lsifier solution containing no test compound were also sprayed on infested plants. After spraying, the pots were placed on their sides on a sheet of white standard mimeograph paper which had been previously ruled to facilitate counting. Temperature and humidity in the test room during the 24 hour holding period were 65-70F.
O and 50-70 per cent, respectively. Aphids which fell onto the paper and were unable to remain standing after being u~righted were considered dead. Aphids remaining on the plants were observed closely for movement and those which were unable to move the length of the body upon stimulator by prodding were considered dead. Per cent mortality was recorded for various concentration levels.

:
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1$1~647 D-10,990 Southern Arm~orm Leaf Spray Test Larvae of the southern armyworm (Prodenia Eridania, (Cram.), reared on Tendergreen bean plants at a temperature of 80~5F. and relative humidity of 50~5 percent, constituted the test insects.
The test com~ounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean pla~ts of ~tandard height and age were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 10 psig. air pressure.
This application which lasted 25 seconds was sufficient to wet plants to run-o~f. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested `~ plants. When dry, the paired leaves were separated and ~ each one was placed in a 9 centimeter Petri dish lined ~ ~ 20 with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes were closed. The closed dishes were labeled and held at 80-85F. for three days. Although the larvae could easily consume the whole leaf within twenty-four hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation by prodding, were considered dead. Per cent mortality was recorded for various concentration levels.

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6~7 D-10,990 Mexican Bean Beetle Leaf SPray Test Fourth instar larvae of the Mexican bean beetle (EPilachna varivestis, Muls.) reared on Tendergreen bean plants at a temperature of 80+5 and 50+5 per cent relative humidity, were the test insects.
The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean plants of standard height and age were placed on a revolving turn- !
; table and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at lO psig air pressure. This application, which lasted 25 seconds was sufficient to wet plants to run-off. As a control, lO0-110 milliliters of a water-acetone-; emulsifier solution containing no test compound were also sprayed on infested plants. When dry, the paired leaves were separated and each was placed in a 9 centimeter Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish, and the dishes were closed. The closed dishes were labeled and held at a temperature of 80+5F. for three days. Although the larvae could easily consume the leaf within 24 to 48 hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation, were considered dead.
Fly Bait Test Four to ~ix day old adult house flies (Musca ; tomestica, ~.) reared according to the specifications of the Chemical Specialties Manufacturing Association (Blue Book, McNair-Dorland Co., NY., 1954; pages 243-244, 261) 15.
' . ` ' .

- ~lQ647 D-10,990 under controlled conditions of 80+5F. and 50~5 per cent relative hmidity, were the test insects. The flies were immo~ilized by anesthetizing with carbon dioxide and twenty five Lmmobilized individuals, males and females, were transferred to a cage consisting of a standard food strainer about five inches in diameter which was inverted over a wrapping-paper-covered surface. The test compounds were formulated by diluting the stock suspension with a 10 per cent (by weight) sugar solution to give a suspension containing 500 parts of test compound per million parts of final formulation, by weight. Ten milliliters of the test formulation were added to a souffle cup containing a one inch square of an absorbent cottom pad. This bait cup was introduced and centered on the blotting paper under the food ætrainer prior to admitt-ing the anesthetized flies. The caged flies were allowed to feed on the bait for twenty four hours, at a temperature of 80+5F. and the relative humidity of 50+5 per cent. Flies which showed no sign of movement on prodding were considered dead.
Mite Foliage SPray Test Adults and nymphal stages of the two~spotted mite (Tetranychus urticae Koch), reared on Tendergreen ~ bean plants at 80~5 per cent relative h~midity, were the ;; test organisms. Infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two- and-a-half inch clay pot. 150-200 mites, a sufficient number for ~:' 16.

, ~ ~ .

~106~7 D-10,990 testing, transferred from the excised leaves to the fresh plants in a period of twenty-four hours. Following the twenty-four hour transfer period, the excised leaves were removed from the infested plants. The test compounds were formulated by diluting the stock suspension with water to give a suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. The potted plants ~one pot per compound) were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulativn by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which lasted for 25 seconds was sufficient to wet the plants to run-off. As a control, 100-110 milliliters of a water solution containing acetone and emulsifier in the same concnetrations as the test compound formulation, but containing no test compound, were also sprayed on infested plants. The sprayed plants were held at 80+5 percent relative humidity for six days, after which a mortality count of motile forms was made. Microscopic examination for m~tile forms was made on the leaves of the test plants. Any individual which was capable of locomotion ` upon prodding, was considered living.
;~ The results of these tests are set forth in Table I below. In these tests the pesticidal activity of ` the compounds against aphid, mite, Southern Armyworm, - Mexican Bean Beetle, and house fly was rated as follows:
A = Excellent control B = Partial control C z No control 17.
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~10647 D-10,990 Mammalian Toxicity Test Certain of these compositions were also evaluated to determine their peroral toxicity to mammals. The animal selected for this experiment was the rat. The test results obtained are expressed in terms of the number of milligrams of compositions per kilogram of : weight of the animal required to achieve a mortality rate of 50 percent (LD50).
The results of all of these tests are set forth in Table I below:

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lllV647 D-10,990 The data in TABLE I clearly illustrates the broad spectrum nigh level pesticidal activity exhibited by the compounds of this invention. It should be under-stood that the pests evaluated are representative of a wider variety of pest which can be controlled by the compounds of this invention.
The compounds contemplated in this invention may be applied as insecticides, miticides and nematocides according to methods known to these skilled in the art.
Pesticidal compositions containing the compounds as the active toxicant will usually comprise a carrier and/or diluent, either liquid or solid.
Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid r.arriers with or without surface acti~e agents. Liquid concen-trates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the acid of suitable surface active emulsifying and dispersing agents.
The choice of dispersing and emulsifying agents ; and the amount employed is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desir-. able to use as little of the agent as is possible, consistent ;
with the desired ~ispersion of the toxicant in the spray so that rain does not re-emulsify the toxicant after it is applied to the plant and wash it off ~, ; the plant. ~onionic, anionic, amphoteric, or cationic --` '` ' 21.
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6~7 D-10,990 dispersing and emulsifying agents may be employed, for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary ammonium compounds, and the like.
In the preparation of wettable powder or dust or granulated compositions, the active ingredient is dis-persed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like. In the formulation of the wettable powders the aforementioned dispersing agents as well as lignosulfonates can be included.
The required amount of the toxicants contem-plated herein may be applied per acre treated in from 1 to 20~ gallons or more of liquid carrier and/or dilue~.t or in from about 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concen-trate will usually vary from about 10 to 95 per cent by weight and in the ~olid formulations from about 0.5 to about ~0 per cent by weight. Satisfactory sprays, dusts, or granules for general use contain from about 1/4 to 15 . pound of active toxicant per acre.
The pesticides contemplated herein prevent attack by insects, nematodes and mites upon plants or other material to which the pesticides are applied, and they have relatively high residual toxicity. With res-; pect to plants, they have a high margin of safety in that when used in sufficient amount to kill or repel the insects, they do not burn or injure the plant, and they resist weathering which includes wash-off caused by rain, ' .;.
~ 22.
, 6~7 D-10,990 decomposition by ultra-violet light, oxidation, or hydrolysis in the presence of moisture or, at least such decomposition, oxidation, and hydrolysis as would materially decrease the desirable pesticidal character-istic of the toxicants or im~art undesirable character-istics, for instance, phytotoxicity, to the toxicants.
The toxicants are so chemically inert that they are compatible with substantially any other constituents of the spray schedule, and they may be used i~ the soil, upon the seeds, or the roots of plants without inj~ring either the seeds or roots of plants. Mixtures of the active compound of this invention may be employed as well as combinations of the active compounds of this invention with other biologically active co~.pounds.

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Claims (11)

WHAT IS CLAIMED IS:

1. 1-Methylsulfinyl-[N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyloxy] acetimidate.

2. S-Methyl-N-?N"-(1-methylsulfinyl-ethylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxy]-thioacetimidate.

3. S-Methyl-N-[N'-[N"-(1-methylsulfonylethyl-idinimooxycarbonyl)-N"-methylaminosulfenyl]-N'-methyl-carbamoyloxy]]thioacetimidate.

4. A method of controlling insects, mites and nematodes which comprises subjecting them to an insectici-dally nematocidally or miticidally effective amount of a compound of the formula:

wherein:
n is 1 or 2;
X is sulfur, sulfinyl or sulfonyl;
R2, R3, R4, R5, R6 and R7 are individually alkyl having from 1 to 8 carbon atoms.

5. A method according to claim 4 wherein R2, R3, R4, R5, R6 and R7 are individually alkyl having from 1 to 5 carbon atoms.

6. A method according to claim 4 wherein R4 and R5 are methyl.

7. A method according to claim 4 wherein R3 and R7 are methyl.

8. A method according to claim 4 wherein the compound is S-methyl-N-?N'-[N"-(1-methylsulfinyl-ethylidiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methylcarbamoyloxyl]]-thioacetimidate

9. A method according to claim 4 wherein the compound is S-methyl-N-[[N'-[N"-(1-methylsulfonylethyl-idiniminooxycarbonyl)-N"-methylaminosulfenyl]-N'-methyl-carbamoyloxy]]thioacetimidate.

10. A method of preparing a compound of the formula:

which comprises reacting a compound of the formula:

with a compound of the formula:

in the presence of an acid acceptor, wherein n is 1 or 2;
R2, R3, R4 and R5 are alkyl having from 1 to 8 carbon atoms.

11. A compound of the formula:

wherein:
n is 1 or 2;
X is sulfur, sulfinyl or sulfonyl;
R2, R3, R4, R5, R6 and R7 are individually alkyl having from 1 to 8 carbon atoms.